Process for the catalytic hydrogenation of a carbon nine resin

Abstract

The application discloses a catalytic hydrogenation method of carbon nine resin, and is characterized in that the method comprises the following steps: (1) placing a Pd-W-Yb / silica gel-activated carbon co-precipitation catalyst in the front half of a fixed bed, placing a Co-Ru-Yb / silica gel co-precipitation catalyst in the rear half of the fixed bed, and reducing by hydrogen; (2) catalytically hydrogenating pretreated carbon nine resin in the fixed bed. Compared with the prior art, the catalytic hydrogenation method of carbon nine resin has high catalytic efficiency and simple process, and the catalytic hydrogenation method can obtain a product with good colority and low bromine value.

Description

Technical Field

[0001] This invention relates to the field of petroleum resin catalytic hydrogenation technology, specifically to a method for catalytic hydrogenation of C9 resin. Background Technology

[0002] C9 is a byproduct of ethylene production via cracking. C9 polymerizes to obtain C9 resin. Hydrogenation catalysis of C9 resin saturates the double bonds and some benzene rings in the resin, and removes residual halogen elements from the polymerization process. This improves the resin's color, photothermal stability, oxidation stability, and UV resistance, enhancing product quality and expanding its applications. With the development of adhesives and sealants, especially in the application of transparent pressure-sensitive tapes, outdoor sealants, disposable hygiene products, medical tapes, road marking paints, and polyolefin modifiers, there is a demand for light-colored, odorless, and stable petroleum resins. C9 resin is one such resin, leading to rapid market demand for hydrogenated C9 resin and driving the development of hydrogenation catalysis technology. The selection of the catalyst is crucial to the quality of the finished product after hydrogenation of C9 resin.

[0003] The raw materials for C9 resin are complex (often containing numerous chromogenic groups, gels, sulfur, and chloride ions). Resin hydrogenation catalysts are mainly classified into two types: noble metal and non-noble metal catalysts. Noble metal catalysts are primarily palladium-based and palladium-platinum-based catalysts. These catalysts offer advantages such as high activity, low start-up temperature, high product yield, and good product quality. However, they are sensitive to poisons such as sulfur and are easily poisoned and deactivated. Non-noble metal catalysts are mostly nickel-based, nickel-tungsten-based, or nickel-molybdenum sulfide-based catalysts supported on diatomaceous earth or alumina-diatomaceous earth. These catalysts have strong sulfur resistance, but their drawbacks include low activity, a still relatively high bromine value in the product, severe hydrogenation degradation, a resin yield of only about 80%, a softening point drop from 120℃ to 90℃, and a short catalyst life. Therefore, current technologies employ different catalysts for staged hydrogenation catalysis of C9 resin.

[0004] The invention patent CN201210451084.1 (publication number CN102924659A), entitled "A Method for Preparing C9 Hydrogenated Petroleum Resin," discloses a two-stage fixed-bed resin hydrogenation method. This method fully utilizes the advantages of two catalyst stages and improves the lifespan of the precious metal catalyst. However, its drawback is that the two catalyst stages use different pressure conditions and cannot be completed in the same fixed bed, resulting in low production efficiency. Furthermore, pressure interference exists during actual operation, affecting the final quality of the C9 resin. The invention patents CN202010128078.7 (publication number CN111333752A), entitled "A Catalytic Method for Hydrogenation of C9 Resin," and CN202010128069.8 (publication number CN111333751A), entitled "A Catalytic Method for Hydrogenation of C9 Resin," employ a single-stage catalysis method, which solves the problem of using different pressure conditions for the two catalyst stages, but still suffers from low efficiency and high pressure.

[0005] In summary, current C9 resin hydrogenation catalysts suffer from poor catalytic performance and complex hydrogenation processes. Therefore, there is a need to develop a C9 resin catalytic hydrogenation method that is both highly efficient and simple. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to provide a catalytic hydrogenation method for C9 resin with high catalytic efficiency and simple process, which can produce products with good color and low bromine value, in light of the current state of the prior art.

[0007] The technical solution adopted by this invention to solve the technical problem is: a catalytic hydrogenation method for C9 resin, characterized by comprising the following steps:

[0008] (1) Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst is placed in the first half of the fixed bed, and Co-Ru-Yb / silica gel coprecipitation catalyst is placed in the second half of the fixed bed, and hydrogen is introduced for reduction.

[0009] (2) The pretreated C9 resin is catalytically hydrogenated in the fixed bed.

[0010] Preferably, the specific preparation method of the Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst is as follows: Prepare a saturated aqueous solution of sodium silicate for later use; dissolve palladium nitrate, tungsten nitrate, and ytterbium nitrate in water to prepare a saturated aqueous solution of metal salts, wherein the molar ratio of Pd:W is 1:0.1 to 1:0.3, and the molar ratio of Pd:Yb is 1:0.02 to 1:0.05. The weight of palladium nitrate, tungsten nitrate, and ytterbium nitrate in the prepared saturated aqueous solution of metal salts is 5 to 10% of the weight of sodium silicate in the saturated aqueous solution of sodium silicate; add 1 / 5 to 1 / 4 of the total weight of nitrates of activated carbon to the above solution, stir evenly, and then add it to the saturated sodium silicate solution. While stirring, introduce carbon dioxide to adjust the pH of the solution to 8 to 9. Separate the precipitate by centrifugation, dry, calcine, and cool to room temperature for later use.

[0011] Furthermore, the stirring method is electric stirring, with a stirring speed of 150-200 revolutions per minute.

[0012] Furthermore, the carbon dioxide is introduced at a rate of 0.5 liters per minute.

[0013] Preferably, the specific preparation method of the Co-Ru-Yb / silica gel coprecipitation catalyst is as follows: A saturated sodium silicate solution is adjusted to pH 1-2 with 5-7 mol / L nitric acid. An aqueous solution of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate is added, with a Co:Ru molar ratio of 1:0.03-1:0.5 and a Co:Yb molar ratio of 1:0.01-1:0.03. The weight of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate in the prepared solution is 5-10% of the weight of sodium silicate. The prepared solution is adjusted to pH 8-9 with a saturated sodium silicate solution to form a precipitate. The precipitate is separated by centrifugation. The separated precipitate is washed with deionized water until neutral, dried, calcined, and cooled to room temperature for later use.

[0014] Furthermore, the drying conditions are as follows: place the item in a drying oven and dry it at 165°C for 5 to 10 hours.

[0015] Furthermore, the roasting conditions are as follows: roasting in a muffle furnace at 600-800°C for 4-8 hours.

[0016] Preferably, the hydrogen reduction conditions in step (1) are: high-purity hydrogen gas is introduced for reduction, the reduction temperature is 200-400℃, and the reduction time is 2-5 hours.

[0017] Preferably, the catalytic hydrogenation conditions in step (2) are: reaction temperature 200–300 °C, reaction pressure 10–18 MPa, and volume hourly space velocity 0.8–1.5 h⁻¹. -1 The volume ratio of hydrogen to resin is 400:1 to 900:1.

[0018] Preferably, the pretreatment conditions in step (2) are as follows: the C9 resin is dissolved in cyclohexane or ethylcyclohexane at a solubility of 5-20 wt%, and the solution is filtered through a clay or diatomaceous earth filter column.

[0019] Compared with the prior art, the advantages of the present invention are as follows:

[0020] (1) The activated carbon silica gel coprecipitation method can ensure a high metal content in the solid catalyst;

[0021] (2) After the activated carbon-silica gel coprecipitate is calcined in a muffle furnace, the activated carbon is burned off, and the resulting catalyst has a relatively large pore size. This catalyst is beneficial for the hydrogenation of C9 resin and increases the hydrogenation efficiency.

[0022] (3) Different catalysts that can react under the same catalytic conditions are placed in the front and back sections of the fixed bed. The Pd-W-Yb / activated carbon-silica gel coprecipitation catalyst mainly removes sulfur, halogens and hydrogenation of double bonds in C9 resin. It is not easily poisoned because of the presence of W. The Co-Ru-Yb / silica gel coprecipitation catalyst mainly performs deep hydrogenation and has the function of further removing other heteroatoms. It can continue to remove residual sulfur and nitrogen in C9 resin. The Co-Ru-Yb / silica gel coprecipitation catalyst has high activity without being poisoned. The two different catalysts have different focuses, but they can play an active role under the same conditions and have complementary effects. The synergistic effect of the two catalysts has achieved good catalytic effect, and simplifies the production process and saves production costs.

[0023] (4) Through the synergistic effect of Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst and Co-Ru-Yb / silica gel coprecipitation catalyst, the bromine value in C9 resin can be reduced from 32.5gBr / 100g to below 3.0gBr / 100g at a relatively high space velocity, and the Gardner color is controlled below 2.5, achieving a good bromine removal effect. Attached Figure Description

[0024] Figure 1 The infrared spectra of C9 resin before catalytic hydrogenation in all embodiments of the present invention are shown.

[0025] Figure 2 The infrared spectrum of C9 resin after catalytic hydrogenation in Example 1 of this invention;

[0026] Figure 3 The infrared spectrum of C9 resin after catalytic hydrogenation in Example 2 of this invention;

[0027] Figure 4 The infrared spectrum of C9 resin after catalytic hydrogenation in Example 3 of this invention;

[0028] Figure 5 The infrared spectrum of C9 resin after catalytic hydrogenation in Example 4 of this invention;

[0029] Figure 6 This is the infrared spectrum of C9 resin after catalytic hydrogenation in Example 5 of the present invention. Detailed Implementation

[0030] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments.

[0031] Example 1:

[0032] (1) Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst was placed in the first half of the fixed bed, and Co-Ru-Yb / silica gel coprecipitation catalyst was placed in the second half of the fixed bed. 99.999% high-purity hydrogen gas was introduced into the fixed bed for reduction. The reduction temperature was 200℃ and the reduction time was 5 hours.

[0033] The preparation of the Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst is as follows: a saturated aqueous solution of sodium silicate is prepared for later use; palladium nitrate, tungsten nitrate, and ytterbium nitrate are dissolved in a saturated aqueous solution, wherein the molar ratio of Pd:W is 1:0.1 and the molar ratio of Pd:Yb is 1:0.03; the weight of palladium nitrate, tungsten nitrate, and ytterbium nitrate in the prepared solution is 5% of the weight of sodium silicate; 1 / 5 of the total weight of activated carbon of nitrate is added to the above solution, and the mixture is stirred electrically (150 rpm) for 8 hours; the above solution is then added to the saturated sodium silicate solution under stirring, and carbon dioxide is introduced at a rate of 0.5 liters per minute to adjust the pH of the solution to 8 while stirring electrically (150 rpm); the precipitate is separated by centrifugation, dried in a drying oven at 165°C for 5 hours, and then calcined in a muffle furnace at 600°C for 8 hours; after calcination, the precipitate is cooled to room temperature for later use.

[0034] The preparation of the Co-Ru-Yb / silica coprecipitation catalyst: A saturated sodium silicate solution was adjusted to pH 2 with 5 mol / L nitric acid. An aqueous solution of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate was added. The molar ratio of Co:Ru was 1:0.03, and the molar ratio of Co:Yb was 1:0.01. The weight of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate in the prepared solution was 10% of the weight of sodium silicate. The prepared solution was adjusted to pH 9 with a saturated sodium silicate solution to form a precipitate. The precipitate was separated by centrifugation. The separated precipitate was washed with deionized water until neutral. The precipitate was dried at 150°C for 3 hours. The dried precipitate was calcined in a muffle furnace at 700°C for 3 hours. After calcination, it was cooled to room temperature for later use.

[0035] (2) C9 resin was dissolved in cyclohexane at a solubility of 15 wt%. The solution was passed through a bleaching clay filter column, allowing insoluble gel, asphaltene, and a small amount of free heavy metals to be adsorbed onto the bleaching clay. The pretreated C9 resin solution was then subjected to catalytic hydrogenation. The hydrogenation catalytic conditions were: reaction temperature 200℃, reaction pressure 18 MPa, and volume hourly space velocity 1.0 h⁻¹. -1 The volume ratio of hydrogen to resin is 400:1.

[0036] Infrared spectrum of C9 resin before catalytic hydrogenation as shown in the figure. Figure 1 As shown, the infrared spectrum of the C9 resin after catalytic hydrogenation in this embodiment is as follows. Figure 2 As shown.

[0037] from Figure 2 It can be seen from the 3019cm -1 The hydrocarbon absorption peaks on the carbon-carbon double bond are significantly smaller than those on the carbon-carbon double bond. Figure 1 3019cm -1 The hydrocarbon absorption peaks on the carbon-carbon double bond, the bromine value of the C9 resin decreased from 32.5 gBr / 100g to 3.0 gBr / 100g, and the Gardner color was 2.5, indicating that the C9 catalyst is effective for the catalytic hydrogenation of the resin.

[0038] Example 2:

[0039] (1) Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst was placed in the first half of the fixed bed, and Co-Ru-Yb / silica gel coprecipitation catalyst was placed in the second half of the fixed bed. 99.999% high-purity hydrogen gas was introduced into the fixed bed for reduction. The reduction temperature was 350℃ and the reduction time was 4 hours.

[0040] The preparation of the Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst is as follows: a saturated aqueous solution of sodium silicate is prepared for later use; palladium nitrate, tungsten nitrate, and ytterbium nitrate are dissolved in a saturated aqueous solution, wherein the molar ratio of Pd:W is 1:0.3 and the molar ratio of Pd:Yb is 1:0.04; the weight of palladium nitrate, tungsten nitrate, and ytterbium nitrate in the prepared solution is 10% of the weight of sodium silicate; activated carbon of 1 / 4 of the total weight of nitrate is added to the above solution, and the mixture is stirred electrically (200 rpm) for 8 hours; the above solution is then added to the saturated sodium silicate solution under stirring, and carbon dioxide is introduced at a rate of 0.5 liters per minute to adjust the pH of the solution to 9 while stirring electrically (200 rpm); the precipitate is separated by centrifugation, dried in a drying oven at 165°C for 10 hours, and then calcined in a muffle furnace at 800°C for 4 hours; after calcination, the precipitate is cooled to room temperature for later use.

[0041] The preparation of the Co-Ru-Yb / silica coprecipitation catalyst: A saturated sodium silicate solution was adjusted to pH 2 with 7 mol / L nitric acid. An aqueous solution of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate was added. The molar ratio of Co:Ru was 1:0.05, and the molar ratio of Co:Yb was 1:0.03. The weight of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate in the prepared solution was 7% of the weight of sodium silicate. The prepared solution was adjusted to pH 9 with a saturated sodium silicate solution to form a precipitate. The precipitate was separated by centrifugation. The separated precipitate was washed with deionized water until neutral. The precipitate was dried at 100°C for 5 hours. The dried precipitate was calcined in a muffle furnace at 600°C for 4 hours. After calcination, it was cooled to room temperature for later use.

[0042] (2) C9 resin was dissolved in cyclohexane at a solubility of 10 wt%. The solution was passed through a diatomaceous earth filter column, allowing insoluble gel, asphaltene, and a small amount of free heavy metals to be adsorbed onto the diatomaceous earth. The pretreated C9 resin solution was then subjected to catalytic hydrogenation. The hydrogenation catalytic conditions were: reaction temperature 300℃, reaction pressure 16 MPa, and volume hourly space velocity 0.8 h⁻¹. -1 The volume ratio of hydrogen to resin is 800:1.

[0043] The infrared spectrum of C9 resin catalytic hydrogenation in this embodiment is as follows: Figure 3 As shown.

[0044] from Figure 3 It can be seen from the 3019cm -1 The hydrocarbon absorption peaks on the carbon-carbon double bond are significantly smaller than those on the carbon-carbon double bond. Figure 1 3019cm -1 The hydrocarbon absorption peaks on the carbon-carbon double bond, the bromine value of the C9 resin decreased from 32.5 gBr / 100g to 0.9 gBr / 100g, and the Gardner color was 0.5, indicating that the C9 catalyst is effective for the catalytic hydrogenation of the resin.

[0045] Example 3:

[0046] (1) The hydrogen reduction conditions for Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst and Co-Ru-Yb / silica gel coprecipitation catalyst in the first half of the fixed bed are as follows: 99.999% high-purity hydrogen gas is introduced into the fixed bed for reduction, the reduction temperature is 400℃, and the reduction time is 5 hours.

[0047] The preparation of the Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst is as follows: a saturated aqueous solution of sodium silicate is prepared for later use; palladium nitrate, tungsten nitrate, and ytterbium nitrate are dissolved in a saturated aqueous solution, wherein the molar ratio of Pd:W is 1:0.2 and the molar ratio of Pd:Yb is 1:0.03; the weight of palladium nitrate, tungsten nitrate, and ytterbium nitrate in the prepared solution is 5% of the weight of sodium silicate; 1 / 4 of the total weight of activated carbon of nitrate is added to the above solution, and the mixture is stirred electrically (180 rpm) for 8 hours; the above solution is then added to the saturated sodium silicate solution under stirring, and carbon dioxide is introduced at a rate of 0.5 L / min to adjust the pH of the solution to 8 under stirring (170 rpm); the precipitate is separated by centrifugation, dried in a drying oven at 165℃ for 8 hours, and then calcined in a muffle furnace at 700℃ for 6 hours; after calcination, it is cooled to room temperature for later use.

[0048] The preparation of the Co-Ru-Yb / silica coprecipitation catalyst: A saturated sodium silicate solution was adjusted to pH 2 with 6 mol / L nitric acid. An aqueous solution of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate was added. The molar ratio of Co:Ru was 1:0.08, and the molar ratio of Co:Yb was 1:0.02. The weight of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate in the prepared solution was 9% of the weight of sodium silicate. The prepared solution was adjusted to pH 9 with a saturated sodium silicate solution to form a precipitate. The precipitate was separated by centrifugation. The separated precipitate was washed with deionized water until neutral. The precipitate was dried at 130°C for 4 hours. The dried precipitate was calcined in a muffle furnace at 650°C for 4 hours. After calcination, it was cooled to room temperature for later use.

[0049] (2) C9 resin was dissolved in ethylcyclohexane at a solubility of 5 wt%. The solution was passed through a diatomaceous earth filter column, allowing insoluble gel, asphaltene, and a small amount of free heavy metals to be adsorbed onto the diatomaceous earth. The pretreated C9 resin solution was then subjected to catalytic hydrogenation. The hydrogenation catalytic conditions were: reaction temperature 250℃, reaction pressure 10 MPa, and volume hourly space velocity 1.5 h⁻¹. -1 The volume ratio of hydrogen to resin is 900:1.

[0050] The infrared spectrum of C9 resin catalytic hydrogenation in this embodiment is as follows: Figure 4 As shown.

[0051] from Figure 4 It can be seen from the 3019cm -1 The hydrocarbon absorption peaks on the carbon-carbon double bond are significantly smaller than those on the carbon-carbon double bond. Figure 1 3019cm -1 The hydrocarbon absorption peaks on the carbon-carbon double bond, the bromine value of the C9 resin decreased from 32.5 gBr / 100g to 1.9 gBr / 100g, and the Gardner color was 1.6, indicating that the C9 catalyst is effective for the catalytic hydrogenation of the resin.

[0052] Example 4:

[0053] (1) The hydrogen reduction conditions for Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst and Co-Ru-Yb / silica gel coprecipitation catalyst in the first half of the fixed bed are as follows: 99.999% high-purity hydrogen gas is introduced into the fixed bed for reduction, the reduction temperature is 380℃, and the reduction time is 3 hours.

[0054] The preparation of the Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst is as follows: a saturated aqueous solution of sodium silicate is prepared for later use; palladium nitrate, tungsten nitrate, and ytterbium nitrate are dissolved in a saturated aqueous solution, wherein the molar ratio of Pd:W is 1:1:0.3, and the molar ratio of Pd:Yb is 1:0.04; the weight of palladium nitrate, tungsten nitrate, and ytterbium nitrate in the prepared solution is 6% of the weight of sodium silicate; 1 / 5 of the total weight of activated carbon of nitrate is added to the above solution, and the mixture is stirred electrically (170 rpm) for 8 hours; the above solution is then added to the saturated sodium silicate solution under stirring, and carbon dioxide is introduced at a rate of 0.5 liters per minute to adjust the pH of the solution to 8 while stirring electrically (160 rpm); the precipitate is separated by centrifugation, dried in a drying oven at 165°C for 6 hours, and then calcined in a muffle furnace at 650°C for 5 hours; after calcination, the mixture is cooled to room temperature for later use.

[0055] Preparation of Co-Ru-Yb / silica gel coprecipitation catalyst: The pH of a saturated sodium silicate solution was adjusted to 2 with 6 mol / L nitric acid. An aqueous solution of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate was added. The molar ratio of Co:Ru was 1:0.2, and the molar ratio of Co:Yb was 1:0.03. The weight of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate in the prepared solution was 6% of the weight of sodium silicate. The pH of the prepared solution was adjusted to 8 with a saturated sodium silicate solution to form a precipitate. The precipitate was separated by centrifugation. The separated precipitate was washed with deionized water until neutral. The precipitate was dried at 130°C for 4 hours. The dried precipitate was calcined in a muffle furnace at 650°C for 4 hours. After calcination, it was cooled to room temperature for later use.

[0056] (2) C9 resin was dissolved in ethylcyclohexane at a solubility of 20 wt%. The solution was passed through a diatomaceous earth filter column, allowing insoluble gel, asphaltene, and a small amount of free heavy metals to be adsorbed onto the diatomaceous earth. The pretreated C9 resin solution was then subjected to catalytic hydrogenation. The hydrogenation catalytic conditions were: reaction temperature 270℃, reaction pressure 14 MPa, and volume hourly space velocity 1.3 h⁻¹. -1 The volume ratio of hydrogen to resin is 500:1.

[0057] The infrared spectrum of C9 resin catalytic hydrogenation in this embodiment is as follows: Figure 5 As shown.

[0058] from Figure 5 It can be seen from the 3019cm -1The hydrocarbon absorption peaks on the carbon-carbon double bond are significantly smaller than those on the carbon-carbon double bond. Figure 1 3019cm -1 The hydrocarbon absorption peaks on the carbon-carbon double bond indicate that the bromine value of the C9 resin decreased from 32.5 gBr / 100 g to 2.5 gBr / 100 g, and the Gardner color was 2.1, suggesting that the C9 catalyst is effective for the catalytic hydrogenation of the resin.

[0059] Example 5:

[0060] (1) The hydrogen reduction conditions for Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst and Co-Ru-Yb / silica gel coprecipitation catalyst in the first half of the fixed bed are as follows: 99.999% high-purity hydrogen gas is introduced into the fixed bed for reduction, the reduction temperature is 350℃, and the reduction time is 5 hours.

[0061] The preparation of the Pd-W-Yb / silica gel-activated carbon coprecipitation catalyst is as follows: a saturated aqueous solution of sodium silicate is prepared for later use; palladium nitrate, tungsten nitrate, and ytterbium nitrate are dissolved in a saturated aqueous solution, wherein the molar ratio of Pd:W is 1:0.15 and the molar ratio of Pd:Yb is 1:0.04; the weight of palladium nitrate, tungsten nitrate, and ytterbium nitrate in the prepared solution is 9% of the weight of sodium silicate; 1 / 4 of the total weight of activated carbon of nitrate is added to the above solution, and the mixture is stirred electrically (200 rpm) for 8 hours; the above solution is then added to a saturated sodium silicate solution under stirring, and carbon dioxide is introduced at a rate of 0.5 L / min to adjust the pH of the solution to 8 under stirring (150 rpm); the precipitate is separated by centrifugation, dried in a drying oven at 165℃ for 9 hours, and then calcined in a muffle furnace at 750℃ for 6 hours; after calcination, the precipitate is cooled to room temperature for later use.

[0062] Preparation of Co-Ru-Yb / silica coprecipitation catalyst: The pH of a saturated sodium silicate solution was adjusted to 2 with 6 mol / L nitric acid. An aqueous solution of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate was added. The molar ratio of Co:Ru was 1:0.4, and the molar ratio of Co:Yb was 1:0.02. The weight of cobalt nitrate, ruthenium nitrate, and ytterbium nitrate in the prepared solution was 8% of the weight of sodium silicate. The pH of the prepared solution was adjusted to 9 with a saturated sodium silicate solution to form a precipitate. The precipitate was separated by centrifugation. The separated precipitate was washed with deionized water until neutral. The precipitate was dried at 150°C for 4 hours. The dried precipitate was calcined in a muffle furnace at 550°C for 5 hours. After calcination, it was cooled to room temperature for later use.

[0063] (2) C9 resin was dissolved in ethylcyclohexane at a solubility of 12 wt%. The solution was passed through a diatomaceous earth filter column, allowing insoluble gel, asphaltene, and a small amount of free heavy metals to be adsorbed onto the diatomaceous earth. The pretreated C9 resin solution was then subjected to catalytic hydrogenation. The hydrogenation catalytic conditions were: reaction temperature 250℃, reaction pressure 17 MPa, and volume hourly space velocity 0.9 h⁻¹. -1The volume ratio of hydrogen to resin is 700:1.

[0064] The infrared spectrum of C9 resin catalytic hydrogenation in this embodiment is as follows: Figure 6 As shown.

[0065] from Figure 6 It can be seen from the 3019cm -1 The hydrocarbon absorption peaks on the carbon-carbon double bond are significantly smaller than those on the carbon-carbon double bond. Figure 1 3019cm -1 The hydrocarbon absorption peaks on the carbon-carbon double bond, the bromine value of the C9 resin decreased from 32.5 gBr / 100g to 1.8 gBr / 100g, and the Gardner color was 1.1, indicating that the C9 catalyst is effective for the catalytic hydrogenation of the resin.

Claims

1. A process for the catalytic hydrogenation of a carbon nine resin, characterized in that It comprises the following steps: (1) Put Pd-W-Yb / silica gel-activated carbon co-precipitation catalyst in the front half of the fixed bed, and Co-Ru-Yb / silica gel co-precipitation catalyst in the back half of the fixed bed, and reduce by hydrogen; (2) Catalytically hydrogenate the pretreated carbon nine resin in the fixed bed; The specific preparation method of the Pd-W-Yb / silica gel-activated carbon co-precipitation catalyst is as follows: prepare a saturated aqueous sodium silicate solution; dissolve palladium nitrate, tungsten nitrate and ytterbium nitrate in water to prepare a saturated aqueous metal salt solution, wherein the molar ratio of Pd:W is 1:0.1-1:0.3, and the molar ratio of Pd:Yb is 1:0.02-1:0.05; the weight of the palladium nitrate, tungsten nitrate and ytterbium nitrate in the prepared saturated aqueous metal salt solution is 5-10% of the weight of the sodium silicate in the saturated aqueous sodium silicate solution; put 1 / 5-1 / 4 of the total weight of the nitrate into the above solution, stir uniformly, then put into the saturated aqueous sodium silicate solution, adjust the pH of the solution to 8-9 by passing carbon dioxide under stirring, separate the precipitate by centrifugation, dry, calcine and cool to room temperature for standby; The specific preparation method of the Co-Ru-Yb / silica gel co-precipitation catalyst is as follows: adjust the saturated aqueous sodium silicate solution to pH 1-2 with 5-7 mol / L nitric acid, pour into an aqueous solution of cobalt nitrate, ruthenium nitrate and ytterbium nitrate, the molar ratio of Co:Ru is 1:0.03-1:0.5, and the molar ratio of Co:Yb is 1:0.01-1:0.03, the weight of the cobalt nitrate, ruthenium nitrate and ytterbium nitrate in the prepared solution is 5-10% of the weight of the sodium silicate, adjust the prepared solution to pH 8-9 with saturated sodium silicate solution to form a precipitate, separate the precipitate by centrifugation, wash the separated precipitate with deionized water until it is neutral, dry, calcine and cool to room temperature for standby.

2. The process for the catalytic hydrogenation of carbon nine resins according to claim 1, characterized in that: The stirring method is electric stirring, and the stirring speed is 150-200 revolutions per minute.

3. The process for the catalytic hydrogenation of carbon nine resins according to claim 1, characterized in that: The carbon dioxide is passed in at a speed of 0.5 liters per minute.

4. The process for the catalytic hydrogenation of carbon nine resins according to claim 1, characterized in that: The drying condition is to put into a drying oven and dry at 165℃ for 5-10 hours.

5. The process for the catalytic hydrogenation of carbon nine resins according to claim 1, characterized in that: The calcination condition is to put into a muffle furnace and calcine at 600-800℃ for 4-8 hours.

6. The process for the catalytic hydrogenation of carbon nine resins according to claim 1, characterized in that: The hydrogen reduction condition in step (1) is to pass in high-purity hydrogen gas for reduction, the reduction temperature is 200-400℃, and the reduction time is 2-5 hours.

7. The process for catalytic hydrogenation of carbon nine resins according to claim 1, characterized by: The catalytic hydrogenation conditions in step (2) are: reaction temperature 200-300°C, reaction pressure 10-18 MPa, volume space velocity 0.8-1.5 h -1 , volume ratio of hydrogen to resin 400:1-900:

1.

8. The process for catalytic hydrogenation of carbon nine resins according to claim 1, characterized by: The pretreatment condition in step (2) is to dissolve the carbon nine resin in cyclohexane or ethyl cyclohexane at a solubility of 5-20wt%, and filter the solution through a white clay or diatomite filter column.

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